Nonradiative deactivation of excited hemicyanines studied with submolecular spatial resolution by time-resolved surface second harmonic generation at liquid-liquid interfaces

J Am Chem Soc. 2011 Mar 2;133(8):2358-61. doi: 10.1021/ja109813j. Epub 2011 Feb 8.

Abstract

The excited-state dynamics of aminostilbazolium dyes is known to be dominated by nonradiative deactivation through large-amplitude motion. In order to identify the coordinate(s) responsible for this process, the excited-state lifetimes of two dialkylaminostyryl-methylpyridinium iodides have been measured at liquid-liquid interfaces using time-resolved surface second harmonic generation. We found that the decay time of the excited-states of both compounds was increasing with the viscosity of the apolar phase, consisting of n-alkanes of varying length, but was unaffected by that of the polar phase, made of water/glycerol mixtures. This indicates that the nonradiative deactivation is associated with the twist of the dialkylaniline group, which is located in the apolar part of the molecule.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Fluorescent Dyes / chemistry*
  • Glycerol / chemistry
  • Molecular Structure
  • Pyridinium Compounds / chemistry*
  • Quinolinium Compounds / chemistry*
  • Stereoisomerism
  • Styrenes / chemistry*
  • Surface Properties
  • Time Factors
  • Water / chemistry

Substances

  • 4-(4-(dibutylamino)styryl)-N-methylpyridinium iodide
  • 4-(4-(dihexadecylamino)styryl)-N-methylquinolinium iodide
  • Fluorescent Dyes
  • Pyridinium Compounds
  • Quinolinium Compounds
  • Styrenes
  • Water
  • Glycerol